In-situ generation of the molecular etcher carbonyl fluoride or any of its variants and its use

ABSTRACT

The molecular etcher carbonyl fluoride (COF 2 ) or any of its variants, are provided for, according to the present invention, to increase the efficiency of etching and/or cleaning and/or removal of materials such as the unwanted film and/or deposits on the chamber walls and other components in a process chamber or substrate (collectively referred to herein as “materials”). The methods of the present invention involve igniting and sustaining a plasma, whether it is a remote or in-situ plasma, by stepwise addition of additives, such as but not limited to, a saturated, unsaturated or partially unsaturated perfluorocarbon compound (PFC) having the general formula (C y F z ) and/or an oxide of carbon (CO x ) to a nitrogen trifluoride (NF 3 ) plasma into a chemical deposition chamber (CVD) chamber, thereby generating COF 2 . The NF 3  may be excited in a plasma inside the CVD chamber or in a remote plasma region upstream from the CVD chamber. The additive(s) may be introduced upstream or downstream of the remote plasma such that both NF 3  and the additive(s) (and any plasma-generated effluents) are present in the CVD chamber during cleaning.

CROSS REFERENCE TO OTHER APPLICATIONS

This application claims benefit of provisional U.S. Application No. 61/743,465, filed Sep. 4, 2012 the disclosure of which is fully incorporated herein by reference.

BACKGROUND OF THE INVENTION

The semiconductor industry has benefited from in-situ dry cleaning procedures made possible by exciting nitrogen trifluoride in a plasma and flowing the plasma effluents to clean interior surfaces of a substrate processing chamber. In-situ cleaning procedures avoid requiring chamber disassembly while still removing undesired substances such as silicon nitride, polycrystalline silicon, silicides and silicon dioxide. Removing these undesired substances before additional substrate processing may reduce defects and control electro-mechanical properties of processed layers.

Nitrogen trifluoride (NF₃), has been widely selected as a precursor to generate fluorine/fluorine radicals in-situ over the use of fluorine (F₂) as a direct result of its ease of handling and cost. The relatively high cost of nitrogen trifluoride combined with speculation that the agent has a high global warming potential (GWP), are causing manufacturers to look for ways to use less NF₃ per preventative maintenance procedure. Thus there is a need for new chamber cleaning agents which more effectively remove contaminants from the interior surfaces of substrate processing chambers and produce more eco-friendly exhaust gases.

Carbonyl Fluoride (COF₂) is an extremely reactive and toxic gas. Carbonyl Fluoride (COF₂) reacts with water (ubiquitous in the environment) to produce hydrogen fluoride, itself a toxic and corrosive gas, and carbon dioxide, and COF₂is difficult to purify. Additionally, there are shelf life concerns in cylinder packaging for COF₂, thus yielding an unstable output that contains a variety of the above mentioned hazardous compounds that may not be fortuitous to a process. Fortunately, the precautions for safe storage, handling and use are well documented; however, the cost for implementing the measures is high versus less hazardous materials. The high cost of manufacture and distribution of carbonyl fluoride (COF₂) are also impacted by its hazardous properties. Combined, these two facts result in an integrated cost of ownership for implementing and using carbonyl fluoride (COF₂) that is commercially questionable. Especially cost prohibitive is retrofitting existing locations where carbonyl fluoride (COF₂) would provide a benefit. In the semiconductor, flat-panel and solar industries, nitrogen trifluoride (NF₃), oxides of carbon (CO_(x) where x=1 or 2) and numerous perfluorocarbon compounds (CyFz) are already is use. Generating Carbonyl Fluoride (COF₂) in-situ from safer, familiar materials allows the technical benefits described herein to be attainable whilst reducing the infrastructure costs and time required to implement and avoids the need of supplying COF2 in a cylinder package.

BRIEF SUMMARY OF THE INVENTION

COF₂ is highly reactive and unstable, and is a very good etch molecule to etch silicon and its compound films. Methods of generating carbonyl fluoride (COF₂) and it's variants in-situ are disclosed herein. The methods of the present invention involve igniting (also referred to herein as striking) and sustaining a plasma, whether it is a remote or in-situ plasma, by stepwise addition of additives, such as but not limited to, a saturated, unsaturated or partially unsaturated perfluorocarbon compound (C_(y)F_(z)) (PFC) and/or an oxide of carbon (CO_(x)) to a nitrogen trifluoride (NF₃) plasma into a chemical deposition chamber (CVD) chamber, thereby generating COF₂. The NF₃ may be excited in a plasma inside the CVD chamber or in a remote plasma region upstream from the CVD chamber. The additive(s) may be introduced upstream or downstream of the remote plasma such that both NF₃ and the additive(s) (and any plasma-generated effluents) are present in the CVD chamber during cleaning.

Embodiments of the invention include methods for the cleaning of deposition chambers in the Liquid Crystal Display (LCD), Flat Panel Display (FPD), semiconductor and related industries at a faster rate, with a secondary advantage of lowering emissions of high global warming potential (GWP) gases such as NF₃. The main ‘etching’ (interchangeable with ‘cleaning’ and/or ‘chamber cleaning’) component in this mixture/mixtures are fluorine/fluorine radical, formed by the remote plasma breakdown of NF₃, and the in-situ generated COF₂. The in-situ generation of COF₂ can be accomplished using a post remote plasma recombination of reactive species. Addition of additives such as, but not limited to saturated, unsaturated or partially unsaturated perfluorocarbon shaving the general formula (C_(y)F_(z)) such as, but not limited to, C₃F₈, C₄F₈, C₂F₆, and C₄F₁₀; oxygen or oxygen containing species such as, but not limited to, carbon monoxide, carbon dioxide, ozone, water, hydrogen peroxide (H₂O₂), hydrofluorinated ethers (HFEs), ethers, ketones, aldehydes, alcohols, carboxylic acids, organic acids (oxalic, acetic, etc.), carbonyls, etc.; and other fluorinated or halogenated species (i.e. SF₆, HF, etc.) to the remote plasma along with traditional chamber clean gas NF₃, results in the in-situ generation of COF₂, which acts as the additional etchant species.

Embodiments of the present invention will serve to enhance commercial processes based on improved quality of product due to better process control, and increase productivity and tool throughput due to reduced down time on process tools.

In addition, new cleaning gases and mixtures are presented that allow for the production of new chemical species that are readily formed in the cleaning process environments and can be removed by conventional vacuum processes. Addition of oxygen and oxygenated species along with intra-oxyhalogenated species are being considered for enhanced cleaning efficiency and cleaning rates.

Additional embodiments and features are set forth in the description that follows, and in part will become apparent to those skilled in the art upon examination of the specification or may be learned by the practice of the disclosed embodiments. The features and advantages of the disclosed embodiments may be realized and attained by means of the instrumentalities, combinations, and methods described in the specification.

BRIEF DESCRIPTION OF THE DRAWINGS

A further understanding of the nature and advantages of the disclosed embodiments may be realized by reference to the remaining portions of the specification and the drawings.

FIG. 1 is a flow chart of an NF₃ plasma initiation and subsequent introduction of additives.

FIG. 2 is a flow chart of an argon plasma initiation, generation of an NF₃ plasma, cessation of Argon and subsequent introduction of additives.

FIG. 3 is a flow chart of an argon plasma initiation and subsequent introduction of additives.

FIG. 4 is a flow chart of introduction of CO_(x) before an existing Argon plasma and subsequent introduction of additives and cessation of Argon.

FIG. 5 is a flow chart of an Argon plasma initiation, addition of an Argon/NF₃ mixture subsequently replacing with a mixture of NF₃ and CO_(x).

FIG. 6 is a flow chart of an Argon plasma initiation, addition of an Argon/NF₃ mixture subsequently replacing with a mixture of NF₃ and additives.

FIG. 7 shows a plot of Etch Rate/Clean Time Results for Pre-Plasma CO₂ Replacement of NF₃ demonstrating no change in etch rate with up to 10% replacement of NF₃ with CO₂.

FIG. 8 shows a plot demonstrating the formation of in-situ COF₂ observed as NF₃ is replaced by CO₂ with a total flow constant around 20 SLPM.

FIG. 9 provides FTIR data comparison of FIGS. 10 and 11.

FIG. 10 shows a plot demonstrating normalized etch rates of in-situ COF₂ observed as NF₃ is replaced by CO₂, pre-plasma replacement at both low and high conductance.

FIG. 11 shows a plot demonstrating etch rates of in-situ COF₂ observed as NF₃ is replaced by CO₂, pre-plasma replacement at both low and high conductance.

FIG. 12 shows a plot demonstrating the formation of in-situ COF₂ observed as CO₂ is added to NF₃ pre-plasma.

FIG. 13 provides FTIR data comparison of FIGS. 14 and 15.

FIG. 14 shows a plot demonstrating normalized etch rates of in-situ COF₂ observed as CO₂ is added to NF₃, pre-plasma at both low and high conductance.

FIG. 15 shows a plot demonstrating etch rates of in-situ COF₂ observed as CO₂ is added to NF₃, pre-plasma at both low and high conductance.

FIG. 16 provides FTIR data of the effect of COF₂ on etch rates.

FIG. 17 shows a plot demonstrating the formation of COF₂ observed as an alternate chamber cleaning molecule, post-plasma CO₂ replacement of NF₃.

FIG. 18 shows a plot demonstrating the formation of COF₂ observed as an alternate chamber cleaning molecule, post-plasma CO₂ addition of NF₃.

FIG. 19 provides FTIR data comparing Formulation 2 (top line), Formulation 1 (middle line) and pure NF₃ (bottom line) when NF₃ is low.

FIG. 20 provides FTIR data comparing Formulation 2 (top line), Formulation 1 (middle line) and pure NF₃ (bottom line) when NF₃ is high.

FIG. 21A provides FTIR data comparing pure NF₃ and PFC in a low NF₃ flow to data presented in FIGS. 21B and 21C.

FIG. 21B provides FTIR data comparing pure NF₃ and PFC in a high NF₃ flow to data presented in FIGS. 21A and 21C.

FIG. 21C provides FTIR data comparing pure NF₃ and PFC and CO₂ in a low NF₃ flow to data presented in FIGS. 21A and 21B.

FIG. 22A demonstrates the effect of a high residence time on the etch rate.

FIG. 22B shows a simplified view of FIG. 22A.

FIG. 23A demonstrates the effect of a low residence time on the etch rate.

FIG. 23B shows a simplified view of FIG. 23A.

In the appended figures, similar components and/or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a dash and a second label that distinguishes among the similar components. If only the first reference label is listed in the specification, the description is applicable to anyone of the similar components having the same first reference label irrespective of the second reference label.

DETAILED DESCRIPTION OF THE INVENTION

In the present invention the generation of COF₂ in-situ under specific process conditions described in detail below, prohibits and significantly reduces the post-plasma recombination formation of NF₃. This generates additional etchant species in COF₂, which is directly responsible for the enhanced cleaning rates and subsequent reduction in consumption of NF₃. In general, the chemistry should be in a mixture as illustrated by:

NF₃+Additive 1+Additive 2+ . . . +Additive n

where n in a value from 1 to 10 and the additives are as follows: Examples of additive gases to form in-situ COF₂ are the following: Addition of saturated, unsaturated or partially unsaturated perfluorocarbons (PFCs) represented by the general formula, C_(y)F_(z), such as, but not limited to C₃F₈, C₄F₈, C₂F₆, and C₄F₁₀; oxygen or oxygen containing species represented by the general formula (CO_(x)) such as carbon monoxide, carbon dioxide, ozone, water, hydrogen peroxide (H₂O₂), hydrofluorinated ethers (HFEs), ethers, ketones, aldehydes, alcohols, carboxylic acids, organic acids (oxalic, acetic, etc.), carbonyls, etc., and other fluorinated or halogenated species (i.e. SF₆, HF, etc.) to the remote plasma along with traditional chamber clean gas NF₃, results in the in-situ generation of COF₂, which acts as the additional etchant species. An additive can have the general formula of B_(s)H_(x)O_(y)A_(z), where B=carbon (C), nitrogen (N), sulfur (S) or mixtures thereof; H=hydrogen; O=oxygen; and A=fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) or mixtures thereof; and w, x, y, z are values from 0 to 30.

The molecular etcher carbonyl fluoride (COF₂) or any of its variants such as, but not limited to, COF₂, COF, OF₂, OF, F₂, F, NOF₂, and NOF, are provided for, according to the present invention, to increase the efficiency of etching and/or cleaning and/or removal of materials such as the unwanted film and/or deposits on the chamber walls and other components in a process chamber or substrate (collectively referred to herein as “materials”). Additionally, the generation of in-situ COF2 allows for the reduction of usage of NF₃, a high global warming potential gas, and this reduces the environmental impact (lowering emissions) of the chamber cleaning process. COF₂ can work together with the available fluorine and/or fluorine radical to make a combined cleaning chemistry that is more effective and efficient than just fluorine and/or fluorine radical alone, which is the typical process when NF₃ is used alone for this purpose.

Essentially, the present invention describes process technology developed for igniting (also referred to herein as striking) a plasma and sustaining the plasma for the cleaning process while and during the flow of the cleaning gases described above and below. This invention also describes the process conditions (i.e., residence time, pressure, flow conductance, etc.) and process tuning required to allow for the creation of in-situ COF₂ and have COF₂ becoming the dominant etching or cleaning species in the process in addition to the fluorine/fluorine radical. Lastly, this invention describes the technology developed for cleaning of substrate materials and/or deposition chambers in the Liquid Crystal Display (LCD), Flat Panel Display (FPD), semiconductor and related industries at a faster rate and includes all film types deposited by such processes.

In order to better understand and appreciate the invention, reference is now made to FIGS. 1-4, which are flow charts describing the steps of striking and sustaining a plasma using NF₃ and additive gasses to produce formation 2, as discussed in greater detail below.

Striking and Sustaining Plasma Using NF₃ and Additive Gases:

As mentioned above, a process of the present invention may be achieved by remote plasma ignition and stabilization. Igniting and sustaining a plasma by the stepwise addition one or more additives such as, but not limited to, an oxide of carbon (CO_(x) wherein x has a value of 1-2) and a saturated, unsaturated or partially unsaturated PFC of formula C_(y)F_(z) to an NF₃ plasma, as shown if FIG. 1. The correct ratio is critical to the working of the present invention. As shown in FIGS. 5, 20, and 21A critical concentrations of COF₂, necessary for etching/cleaning, is only generated upon achieving a specific ratios of NF₃ the oxide of carbon (CO_(x) wherein x has a value of 1-2) and PFC additives. FIG. 2 demonstrates and alternative embodiment wherein a plasma is ignited in argon (Ar) and then NF₃ replaces the Ar to create an NF₃ plasma. The NF₃ flow is set to the desired flow, which is specific to each semiconductor process. An oxide of carbon (CO_(x) wherein x has a value of 1-2) and a saturated, unsaturated or partially unsaturated PFC of formula C_(y)F_(z) is gradually introduced in a stepwise fashion to the NF₃ plasma until the desired concentration and/or flow is reached, which again is specific to each semiconductor process. Additive gases such as CO₂ or CO in the remote plasma unit along with NF₃ undergo plasma dissociation. Subsequently, by recombination, COF₂ is generated in-situ of the etch chamber. COF₂ is highly reactive and unstable, and is a very good etch molecule to etch silicon and its compound films. The mechanism of enhancing the etch rate is discussed as follows for formulation 1 (CO₂+NF₃) and is not limited to information and mechanisms shown:

The chemistry involved in the plasma dissociation of pure NF₃ is listed below:

NF₃→N+3/2F₂

Without any additive gases, post-plasma, the recombination reaction is as follows:

N+3/2F₂→NF₃

CO₂, when used as additive, breaks down in the plasma as follows:

CO₂→CO+O

CO₂→C+2O

The in-situ generation chemistries post-plasma of NF₃ and CO₂ additive are listed below:

CO+F→COF

COF+F→COF₂

CO+F₂→COF₂

C+2F₂→CF₄

The primary post-plasma species generated is COF₂ and this particular embodiment is referred to herein as “Formulation 1” CF₄ is a minor component which may or may not enhance the etch/cleaning rates significantly. The key role of CO₂ after plasma breakdown is its ability to scavenge fluorine and form COF₂ while minimizing the recombination formation of inert NF₃, which by itself is not an etchant. This enhances the available etchant in the mixture (COF₂, fluorine and fluorine radicals) thus increasing the etch rates.

Alternatively, COF₂ and its variants may be generated by igniting and sustaining a plasma by stepwise addition of CO₂, NF₃ and PFCs to an argon plasma, as shown in FIG. 3. Alternatively, FIG. 4 demonstrates a plasma ignited with high flow of argon (AR) as discussed previously (target flow for clean chemistry). CO₂ additive gas is added pre-plasma. Subsequently, NF₃ and any PFCs are added. Once the plasma is stable, argon is cut-off completely, just sustaining the plasma. This particular embodiment, Formulation 2, focuses on enhancing the generation of etchant species, namely COF₂, in-situ for the cleaning process, in addition to fluorine/fluorine radicals formed by the plasma dissociation of NF₃. The key innovation of Formulation 2 is the addition of PFCs to NF₃ which results in the increase of in-situ generation of COF₂ while allowing for a larger CO₂ flow/dilution and reducing NF₃ concentrations/flows. During plasma dissociation of PFC molecules, additional fluorine/fluorine radicals are generated which leads to in-situ generation of COF₂ by recombination with the CO radical. Saturated, unsaturated or partially unsaturated PFC molecules of the general formula (C_(y)F_(z)) are chosen with a high fluorine content/molecule such as, but not limited to C₂F₆, C₃F₈, C₄F₈, and C₄F₁₀. These additive molecules have the ability to generate more fluorine per molecule than NF₃. The distinction from prior art is that this additive is solely for the purpose of increased in-situ generation of COF₂. Any other plasma breakdown fragments of the PFCs are only minor contributions to the actual etch/cleaning process.

As an example case, the chemistries involved with C₃F₈ addition to NF₃ are discussed below and this particular chemistry is referred to as Formulation 2 (CO₂+NF₃+PFC). The mechanisms discussed as follows are not limited to information and mechanisms shown:

The chemistry involved in the plasma dissociation of pure NF₃ is listed below:

NF₃→N+3/2F₂

Without any additive gases, post-plasma, the recombination reaction is as follows:

N+3/2F₂→NF₃

CO₂, when used as additive, breaks down in the plasma as follows:

CO₂→CO+O

CO₂→C+2O

C₃F₈ breakdown in plasma can be listed as follows (not stoichiometric, for illustration only):

nC₃F₈ →aCF₃ +bCF₂ +cCF+dF

The in-situ generation chemistries post-plasma of NF₃, CO₂ and (C₃F₈ as additive are listed below:

CO+F→COF

COF+F→COF₂

CO+F₂→COF₂

CF₃+F→CF₄

CF₂+F₂→CF₄

C+2F₂→CF₄

The primary post-plasma species generated is COF₂, CF₄ is a minor component which may or may not enhance the etch/cleaning rates significantly. No other significant fragments of C₃F₈ breakdown were observed. The key role of CO₂ after plasma breakdown is its ability to scavenge fluorine from NF₃ and C₃F₈ breakdown and form COF₂ while minimizing the recombination formation of inert NF₃ and CF₄, which by itself are not etch contributing molecules/fragments. This enhances the available etchant in the mixture thus significantly increases the etch/cleaning rates.

COF₂ and its variants may also be generated by igniting and sustaining a remote plasma by addition of NF₃+CO₂ to an Ar+NF₃ plasma, shown in FIG. 5. As discussed previously, a plasma is ignited in argon (Ar) and then a blend of Ar and NF₃ replaces the Ar to create a blended Ar+NF₃ plasma. This plasma is replaced by a direct mixture of NF₃+CO₂, where both species are at the desired concentrations and/or flows. The concentration of Ar and NF₃ are set to be able to ignite a plasma without fault and are specific to each semiconductor or LCD/FPD process tool Alternatively, shown in FIG. 6, a plasma is ignited in argon (Ar) and then a blend of Ar and NF₃ replaces the Ar to create an blended Ar+NF₃ plasma. This plasma is replaced by a direct mixture of NF₃+CO₂+PFCs, where all species are at the desired concentrations and/or flows. The concentration of NF₃, CO₂ and PFCs are typically in the range of about 1%-99% NF₃, 2%-99% CO₂, and 0%-99% PFC; however, the ranges may be about 2%-75% CO₂ and preferably 5%-50% CO₂ and 0%-50% PFC or preferably 0%-20% PFC, wherein the percentage of NF₃ makes up the remaining balance.

The plasma process described above relates to both remote and in-situ plasma generation. For remote plasma generation, a variety of plasma sources such as, but not limited to, inductively coupled plasma (ICP), microwave plasmas, torroidal plasma generators, etc., and any alterations, variations, or additions to those plasma configurations to make the etching or cleaning more efficient and/or uniform may be implemented. For in-situ generation, this can be a variety of plasma sources, such as, but not limited to ICP, conductively coupled plasma (CCP), microwave, etc., and any alterations, variations, or additions to those plasma configurations to make the etching or cleaning more efficient and/or uniform. It should be noted that the increased resistivity of the NF₃+Additives mixtures may affect the power of the plasma and this increase in power may also aid in increasing the etching or cleaning efficiency.

Activation Energy Sources

It should be noted that dissociation of molecules to atoms and or radicals can be effected by energy sources other than plasma. Energy sources for the activation of in-situ carbonyl fluoride (COF₂) generation by reaction of nitrogen trifluoride (NF₃), an oxide of carbon (CO_(x), where x=1-2) and a saturated, unsaturated, or partially unsaturated perfluorocarbon compound with the general formula of C_(y)F_(z) include plasma, electromagnetic radiation, pressure waves (e.g. sound that propagate through compressible gas mixture), elevated temperatures or direct contact with hot surfaces can also break apart molecules. Hot surface energy sources may include but are not limited to hot wires, heated surfaces, furnaces, and flames. Different frequency domains of electromagnetic radiation may be used to provide energy for dissociation. Frequencies such as, but not limited to radio waves, microwaves, infrared radiation, visible light, ultraviolet radiation, X-rays, alpha, beta, and gamma rays may be used independently or combined to cause the reaction or species. Plasma energy sources may include but are not limited to DC coupled, inductively coupled, capacitively coupled, microwave, glow discharge, wave-heated or electrodeless. The location of the plasma may be local or remote to the point that is COF₂ generated. The rate of the reaction may also be increased by the use of catalysts.

Regardless of the process described above for the generation of COF₂ the other significant factors in enhancing the etch rate/cleaning times is the residence time of the molecule in the chamber and the chamber pressure. With lower residence times, the etchant species does not have sufficient time to interact with the surface (residual films) and subsequently etch them. By increasing the residence time (can be accomplished by reducing the conductance, reducing number of vacuum pumps pulling the gases out etc.), there is sufficient interaction time for the in-situ generated etchant species to clean the residual films. Increasing the post-remote plasma residence time of the process gases (this increases the time of interaction between radicals to allow higher COF₂ generation). FIGS. 7-9, 11-13, 14, 20 and 21 demonstrate this effect. Pressure, on the other hand, is a measure of how many times the molecule impinges on the surface. By having lower pressures, the probability of the molecule impinging on the residual film surface is lower, hence a lower etch rate. Higher pressures increase the number of times the in-situ chemistry interacts with a surface, and thus increases the cleaning rate. By having a suitable pressure, wherein the in-situ generated etchant species can have sufficient interaction/impingement with the residual film surface, etch rate/cleaning times can be enhanced.

Although the primary focus of this disclosure is for the in-situ generation of COF₂, mixed halogenated versions and derivatives of these molecules are also possible depending on the additives used in the process.

The plasma process described in this invention relates to both remote and in-situ plasma generation in all their various forms.

It should be noted that the increased resistivity of the NF₃+Additives mixtures may affect the power of the plasma and this increase in power may also aid in increasing the etching or cleaning efficiency.

Chamber Cleaning Process Improvements or Enhancements Demonstrated by the Generation of COF₂:

Methods of cleaning a process chamber with carbonyl fluoride (COF₂) are described. The present invention describes technology developed for the cleaning of deposition chambers and/or substrates at a faster rate, with a secondary advantage of lowering emissions of high global warming potential (GWP) gases such as NF₃. The main ‘etching’ (interchangeable with ‘cleaning’ and/or ‘chamber cleaning’) components in this mixture/mixtures are fluorine/fluorine radical, formed by the remote plasma breakdown of nitrogen trifluoride (NF₃), and the in-situ generated carbonyl fluoride.

More specifically, this process generates the cleaning/etching agent COF₂ which may be used in the cleaning of deposition chambers in the LCD, FPD, semiconductor and related industries for cleaning post-deposition residues inside the chamber including chamber walls, showerhead, wafer susceptor, etc. These deposition processes may include, but are not limited to the deposition of thin films of silicon, silicon dioxide, silicon nitride, silicon carbo-nitride, silicon oxy-nitride, silicon oxy-carbo-nitride, TEOS, BPSG, doped oxides, metal nitrides (TiN, TaN, etc.) metal oxides (TiO₂, etc.), etc. The invention can also be used for substrate and/or surface cleaning, modification and/or preparation. Hereinafter the surfaces to be cleaned and/or etched are collectively referred to herein as materials. Examples of materials that would benefit from such cleaning, modification, and/or preparation by the invention chemistry and process include metals, metal compounds, semiconductor substrates, PV substrates, LED/OLED, MOCVD substrates, III-V materials, etc.

The methodologies for generating COF₂ have been disclosed in detail above and specific examples are discussed below; however, in general the methods involve igniting and sustaining a plasma by the stepwise addition of one or more additives. A plasma is ignited in argon (Ar) and then NF₃ replaces the Ar to create an NF₃ plasma. The NF₃ flow is set to the desired flow and the additive is gradually introduced to the NF₃ plasma until the desired concentration and/or flow is reached. Additive gases such as CO₂, CO and/or PFCs in the remote plasma unit along with NF₃ undergo plasma dissociation. Subsequently, by recombination, COF₂ is generated in-situ of the etch chamber. COF₂ is highly reactive and unstable, and is a very good etch molecule to etch silicon and its compound films.

The NF₃ may be excited in a plasma inside the chamber or in a remote plasma region upstream from the chamber. The in-situ generation of COF₂ can be accomplished using a post remote plasma recombination of reactive species or recombination of the species in an in-situ plasma environment. The additive(s) may be introduced upstream or downstream of the remote plasma such that both NF₃ and the additive(s) (and any plasma-generated effluents) are present in the chamber during cleaning. The generation of COF₂ enhances the chamber-cleaning effectiveness and simultaneously allows less NF₃ to be used and discarded. Exemplary chambers may include chemical vapor deposition (CVD)) chambers, physical vapor deposition (PVD) chambers, and atomic-layer deposition (ALD) chambers, among other kinds of process chambers.

The additive(s) may be introduced downstream from the remote plasma region such that, in essence, only the NF₃ passes through plasma excitation in embodiments of the invention. Plasmas may also be present in both regions. In some embodiments, a hot surface such as a filament is used in place of a plasma in any of the plasma configurations described. The COF₂ formed by the plasma dissociation may be referred to as the cleaning mixture. The cleaning mixture may also include a non-reactive gas such as nitrogen (N₂), helium (He), neon (Ne) and/or argon (Ar), as well as mixtures thereof. Non-reactive gases may help to statistically reduce the chance for NF₃ fragments to recombine and form an NF₃ molecule. Some non-reactive gases may also assist in igniting and maintaining the plasma.

Silicon-containing contaminants are typical contaminants which COF₂ treatments are intended to remove. The silicon-containing contaminants may include deposits of silicon oxide on interior surfaces of a deposition chamber during a preceding silicon oxide substrate deposition process. Contaminants may also include silicon nitrides, poly-silicons, silicides, silicon oxy-nitrides, and doped silicon glasses, among other contaminants. As noted above, an exemplary processing chamber for use with the cleaning procedures described include a chemical vapor deposition (CVD) chamber. The claimed cleaning methods may find utility for other chambers such as PVD and ALD chambers. A substrate may or may not be present in the deposition chamber during the cleaning procedure. NF₃ introduction into the exhaust system may be reduced both by decreasing the amount of NF₃ needed to remove a given contaminant and by reducing the recombination of NF₃ fragments to form NF₃. Traditional abatement methods may be performed on any remaining NF₃ emissions including combusting the emissions and/or treating them with a water scrubber. Combining the methods described herein with the traditional abatement methods may achieve a further reduction in NF₃ released into the atmosphere.

The invention is further illustrated by the following non-limited examples. All scientific and technical terms have the meanings as understood by one with ordinary skill in the art. The methods may be adapted to variation in order to produce compositions embraced by this invention but not specifically disclosed. Further, variations of the methods to produce the same compositions in somewhat different fashion will be evident to one skilled in the art.

EXPERIMENTAL Formulation I Experiments Terminology

“Pre-Plasma” indicates that NF₃ and CO₂ were placed through the plasma together, thus dissociating each species to cause interactions.

“Post-Plasma” indicates that NF₃ was placed through the plasma to dissociate and CO₂ was added downstream of the plasma effluent.

“CO₂ Replacement” indicates that NF₃ was replaced by CO₂ in the process keeping the total flow constant.

“CO₂ Addition” indicates that CO₂ was added on top of a constant flow of NF₃ in the process.

Experiments were conducted to see the effects of adding CO₂ to NF₃ in a remote plasma on the chamber cleaning time/etch rate and chamber emissions. CO₂ was added to NF₃ both pre-plasma (i.e. NF₃ and CO₂ create a plasma together) and post-plasma (i.e. CO₂ interacts with the NF₃ plasma products). A clean time/etch rate was determined for various NF₃+CO₂ recipes based on the removal of a 300 nm silicon nitride deposition. An example of this can be seen in FIG. 7.

-   -   1. Time-of-flight mass spectrometry (TOFMS) and FTIR data were         taken just downstream of the chamber.     -   2. The FTIR data has been reprocessed with calibrations taken at         low pressure.     -   3. Silicon nitride substrates or deposited films were used at         obtain etch rate results         The remote plasma was self-adjusting of the power needed to         sustain a plasma

Two sets of experiments were conducted:

-   -   1. Low conductance regime         -   a. Four sets of experiments each for CO₂ replacement and             addition     -   2. High conductance regime         -   a. One set of experiments for CO₂ replacement and addition

First Run of Experiments: (Low Conductance)

-   -   Two experiments were performed at higher NF₃ flows and higher         pressure (Runs 1 and 2) and two experiments were performed at         lower NF₃ flows and same pressures as runs 1 and 2 (Runs 3 and         4).

Data Demonstrated Excellent Reproducibility of all Experiments

-   -   Second run of experiments: (high conductance)         One set of experiments for replacement as well as addition of         CO₂ were conducted keeping same flow rates and process pressures         as runs 1 and 2 (low conductance).

COF₂ Etching

-   -   COF₂ is in-situ generated from NF₃ and CO₂ (Formulation 2—add         PFC also).     -   Reaction time is important for COF₂ generation.     -   Higher residence time in chamber for reactant species=Higher         COF₂ amount generated=Higher etch rates.     -   Higher residence time=Lower conductance.

Example 1 Pre-Plasma CO₂ Replacement of NF₃

Experiments were performed having various parameters all of which can be seen in FIGS. 6. Table 1 details the experimental setup parameters for pre-plasma replacement of NF₃—run 1.

All etch times 1 minute unless noted otherwise

Plasma operated at minimum power to sustain plasma

TABLE 1 Total flow 1000 (sccm) Initial RF Etch rate (nm/min) NF₃ Fraction Thickness Pressure Power Reflecto- Profilo- (sccm) CO₂ CO₂ (μm) (mTorr) (W) meter meter Average 1000 0.0 0 1947.44 860 5000 1250 1000 1125 960 40.0 0.04 1940.48 876 5000 1460 1224 1342 920 80.0 0.08 1905.44 895 5800 1800 1588 1694 870 130.0 0.13 1913.15 880 6000 1830 1621 1725.5 820 180.0 0.18 1967.19 860 6400 1720 1559 1639.5 750 250.0 0.25 1947.86 835 6600 1670 1477 1573.5

The results of the Run 1 experiment are as follows:

Maximum etch rate: 1725 nm/min

CO₂ fraction @ max etch rate: 13%

NF₃ fraction @ max etch rate: 87%

Edge effect—Difference in reflectometer and profilometer etch rates. Etch rate closer to mask edge is slower than bulk etch rate (not RIE).

Pre-Plasma Replacement of NF₃—Run 2, the results of which are as follows:

Maximum etch rate: 1736 nm/min

CO₂ fraction @ max etch rate: 18%

NF₃ fraction @ max etch rate: 82%

Pre-Plasma Replacement of NF₃—Run 3 was performed To check effects of total gas flow, the gas flow rates were reduced by half:

CO₂ replacement:

-   -   500 sccm total flow

CO₂ addition:

-   -   500 sccm constant flow of NF₃     -   Additional CO₂ added to constant NF₃

Pre-Plasma Replacement of NF₃—Run 3, the results of which are as follows:

Maximum etch rate: 1634 nm/min

CO₂ fraction @ max etch rate: 13%

NF₃ fraction @ max etch rate: 87%

Pre-Plasma Replacement of NF₃—Run 4 was performed to check effects of pressure, the gas flow rates were kept constant as run 3, but throttle valve wide open to get process pressures ˜600 mTorr:

CO₂ replacement:

-   -   500 sccm total flow

CO₂ addition:

-   -   500 sccm constant flow of NF₃     -   Additional CO₂ added to constant NF₃

Pre-Plasma Replacement of NF₃—Run 4, the results of which are as follows:

Maximum etch rate: 1142 nm/min

CO₂ fraction @ max etch rate: 8%

NF₃ fraction @ max etch rate: 92%

Pre-Plasma Replacement of NF₃—Run 5 was performed with the following parameter changes:

-   -   Alter residence times of reactants in the cleaning chamber     -   To check effects of residence time, the flow conductance to the         vacuum pump was increased     -   Lines changed from KF-40 (˜1.5″ ID) to ISO-100 (˜4″ ID), thereby         increasing conductance significantly         All other process parameters kept constant as Run 1, including         pressure and flow rates.

Data Summary—Normalized Etch Rates to pure NF₃ etching, Low Conductance: Average of Runs 1, 2, 3, 4 and High Conductance—Run 5 are shown in FIG. 10.

Data Summary—Absolute Etch Rates, Low Conductance: Average of Runs 1, 2, 3, 4 and High Conductance—Run 5 are shown in FIG. 11.

FTIR Data Comparison, Pre-plasma Replacement—Run 1 and 5 is shown in FIG. 9.

Absorbance from COF₂—almost identical in both run 1 and 5

Residual CO₂ absorbance—almost identical

Etch rate of Run 1 higher than Run 5.

Primary cause—Longer residence times inside chamber in Run 1

Longer residence times inside chamber→Higher COF₂ in chamber

Higher COF₂ in chamber→Higher etch rate

Similar COF₂ seen in FTIR due to longer time to sampling

Pre-Plasma Replacement

-   -   The following results are for pre-plasma replacement of NF₃ with         CO₂ the results of which are summarized in Table 2.

TABLE 2 Run # Residence time Conditions 1 High Total flow 1SLPM; Pressure constant 2 High Total flow 1SLPM; Pressure constant 3 High Total flow 500 sccm; Pressure constant 4 High Total flow 500 sccm; low pressure 5 Low Total flow 1SLPM; Pressure constant

Example 2 Pre-Plasma CO₂ Addition to NF₃

Experiments were performed having various parameters all of which can be seen in FIG. 12. Table 3 details the experimental setup parameters for Pre-Plasma Addition of CO₂—run 1.

Etch rate at 0.25 fraction CO₂ projected value.

Actual etch time=45 sec

$\begin{matrix} {{{Actual}\mspace{14mu} {etch}\mspace{14mu} {rates}} = {1404({Profilometer})}} \\ {= {1590({Reflectometer})}} \end{matrix}$

TABLE 3 Initial RF Etch rate (nm/min) NF₃ CO₂ Fraction Thickness Pressure Power Reflecto- Profilo- (sccm) (sccm) CO₂ (μm) (mTorr) (W) meter meter Average 1000 0.0 0 1929.18 878 5000 1130 903 1016.5 1000 41.7 0.04 1971.3 926 5400 1720 1537 1628.5 1000 87.0 0.08 1964.87 938 5800 1840 1650 1745 1000 149.4 0.13 1954.65 954 6200 1930 1747 1838.5 1000 219.5 0.18 1957.6 976 6600 1980 1834 1907 1000 333.3 0.25 1951.8 995 7000 2120 1872 1996

Pre-Plasma Addition of CO₂—Run 1, the results of which are as follows:

Maximum etch rate: 1926 nm/min

CO₂ fraction @ max etch rate: 25%

NF₃ fraction @ max etch rate: 75%

Pre-Plasma Addition of CO₂—Run 2, the results of which are as follows:

Maximum etch rate: 1926 nm/min

CO₂ fraction @ max etch rate: 25%

NF₃ fraction @ max etch rate: 75%

Pre-Plasma Addition of CO₂—Run 3, the results of which are as follows:

Maximum etch rate: 1936 nm/min

CO₂ fraction @ max etch rate: 25%

NF₃ fraction @ max etch rate: 75%

Pre-Plasma Addition of CO₂—Run 4, the results of which are as follows:

Maximum etch rate: 1936 nm/min

CO₂ fraction @ max etch rate: 25%

NF₃ fraction @ max etch rate: 75%

Pre-Plasma Addition of CO₂—Run 5 was performed with the following parameter changes:

-   -   Alter residence times of reactants in the cleaning chamber.     -   To check effects of residence time, the flow conductance to the         vacuum pump was increased.     -   Lines changed from KF-40 (˜1.5″ ID) to ISO-100 (˜4″ ID), thereby         increasing conductance significantly.         All other process parameters kept constant as Run 1, including         pressure and flow rates.

Formulation 1 Pre-Plasma Addition

Data Summary—Normalized Etch Rates to pure NF₃ etching, Low Conductance: Average of Runs 1, 2, 3, 4 and High Conductance—Run 5 are shown in FIG. 14.

Data Summary—Absolute Etch Rates, Low Conductance: Average of Runs 1, 2, 3, 4 and High Conductance—Run 5 are shown in FIG. 15.

FTIR Data Comparison

Pre-plasma Addition—Run 1 and 5 is shown in FIG. 13

Absorbance from COF₂—almost identical in both run 1 and 5.

Residual CO₂ absorbance—almost identical.

Etch rate of Run 1 higher than Run 5.

-   -   Primary cause—Longer residence times inside chamber in Run 1.     -   Longer residence times inside chamber→Higher COF₂ in chamber.     -   Higher COF₂ in chamber→Higher etch rate.     -   Similar COF₂ seen in FTIR due to longer time to sampling.

FIG. 14 shows data collected of the effect of COF₂ on etch rates.

Results in Table 4 are for pre-plasma addition of CO₂ to NF₃.

TABLE 4 Run # Residence time Conditions 1 High NF₃ 1SLPM; Pressure constant 2 High NF₃ 1SLPM; Pressure constant 3 High NF₃ 500 sccm; Pressure constant 4 High NF₃ 500 sccm; low pressure 5 Low NF₃ 1SLPM; Pressure constant

Example 3 Post-Plasma CO₂ Replacement of NF₃

Post-Plasma CO₂ Replacement of NF3, FTIR Chamber Effluent Data shown in FIG. 15.

Post-Plasma CO₂ Addition to NF₃, FTIR Chamber Effluent Data shown in FIG. 16.

Summary

TABLE 5 Pre-Plasma Formulation 1 Post-Plasma Formulation 1 CO₂ Replacement CO₂ Replacement Replaced NF₃ with CO₂ from 0 to Replaced NF₃ with CO₂ from 0 to 20% 40% Total flow constant at 20 SLPM Total flow constant at 30 SLPM CO₂ Addition CO₂ Addition Added CO₂ on top of constant Added CO₂ on top of constant NF₃ NF₃ flow from 0 to ~17% flow from 0 to ~60% NF₃ flow constant at 20 SLPM NF₃ flow constant at 30 SLPM

Explanation of Calculation of Clean Times

Of all the Formulation 1 scenarios tested, the pre-plasma NF₃+CO₂ mixtures worked best.

Of the two pre-plasma experiments, the CO₂ replacement of NF₃ provides the maximum benefit.

Up to 10% replacement of NF₃ is possible while maintaining the etch rate/clean time.

A ˜40% reduction in NF₃ emissions is realized.

The impact of GWP by-products is shown to have negligible impact on the total MMTCE contributions.

The disclosed FTIR and TOFMS data validate and support the above mentioned statements.

Formulation 1—Conclusions

-   -   Pure NF₃ etching—Fluorine dominant etchant.

Formulation 1—Fluorine and COF₂ dominant etchant species.

-   -   Low residence time—Optimized for NF₃ etching.     -   High residence time—Optimized for COF₂ etching.     -   CO₂ addition has higher etch rate than CO₂ replacement (due to         higher COF₂ generated).     -   No significant variation with flow rate (excess gas compared to         cleaning surface/sample).     -   Minimal effect from process pressure (in the ranges explored:         <20% variation).     -   FTIR data suggests almost identical amounts of COF₂ generation         from the absorption spectra (downstream of etching chamber) for         lower and higher chamber residence times.     -   Formation of COF₂ downstream of etching chamber does NOT help in         chamber cleaning, hence the lower etching rates.

Formulation 2 Experiments Example 4

Formulation 2: How is it different than Formulation 1?

Formulation 1→NF₃+CO₂

-   -   ˜10% reduction in NF₃ consumption with current hardware         configuration     -   Maintains cleaning rates

New requirements:

-   -   Increase cleaning rates up to 3×     -   Reduce NF₃ consumption >15-20%, 25%+preferred

Experimental limitations:

-   -   Current hardware configuration

Formulation 2→NF₃+CO₂+C₃F₈

-   -   Ternary mixture     -   ˜40-50% reduction in NF₃ consumption     -   ˜40-50% increase in cleaning rates

Etching species:

-   -   F and F₂     -   COF₂ (In-situ generation; dominant etchant species)     -   CF₄ (minimal effect)

C₃F₈ with CO₂ and NF₃ breaks down into COF₂ and CF₄ in the plasma;

Confirmed with in-situ FTIR analyses

Design of experiments:

-   -   Central composite design     -   Face centered design     -   3 factors (NF₃, CO₂, C₃F₈)     -   Two replicates to study reproducibility/variance     -   Response factor—Etch rate of PECVD Silicon Nitride samples

Experimental procedure:

-   -   Samples masked using Kapton tape     -   Etch time=30 s     -   Etch rate determination:         -   Reflectometer measurements before etching         -   Reflectometer after etching

Analysis of results/response factor:

-   -   Maximum of |R|²     -   f-statistic significance     -   Plot response surface—NF₃vs C₃F₈; vary CO₂

Formulation 2 Design Of Experiments: Central Composite—FCC design

3 Factors 3 Centerpoints

Quadratic Model with 10 items Response=b0+b1*NF₃, sccm+b2*CO₂, sccm+b3 C₃F₈, sccm+b4*NF₃, sccm*NF₃, sccm+b5*CO₂, sccm*CO₂, sccm*b6*C₃F₈, sccm*C₃F₈, sccm+b7*NF₃, sccm*CO₂, sccm+b8*NF₃, sccm*CF₃F₈, sccm*C₃F₈, sccm+b9*CO₂, sccm*C₃F₈, sccm.

TABLE 6 NF₃, CO₂, C₃F₈, RF % % % Exp # sccm sccm sccm Resp 1 Initial Final Power NF₃ CO₂ C₃F₈ 125 500 700 0 1416.96 1903.31 1194.83 8000 41.7 58.3 0.0 126 500 0 300 1004.16 1935.26 1433.18 7200 62.5 0.0 37.5 127 750 350 150 1987.6 1945.45 951.65 8200 60.0 28.0 12.0 128 1000 700 0 2707.58 1948.67 594.88 8200 588.8 41.2 0.0 129 750 700 150 2901.74 1924.9 474.03 9200 46.9 43.8 9.4 130 1000 0 300 1397.36 1950.23 1251.55 7400 76.9 0.0 23.1 131 750 700 150 1490.62 1943.16 1197.85 6800 83.3 0.0 16.7 132 500 0 300 1911 1912.99 957.49 9800 33.3 46.7 20.0 133 500 0 0 1606.78 1929.66 1126.27 4800 100.0 0.0 0.0 134 500 350 150 1757.22 1934.38 1055.77 8400 50.0 35.0 15.0 135 1000 350 150 2243.76 1933.93 812.05 8200 66.7 23.3 10.0 136 750 350 300 1310.94 1946.66 1291.19 8800 53.6 25.0 21.4 137 750 350 150 2152.02 1926.72 850.71 8400 60.0 28.0 12.0 138 750 350 150 2236.44 1903.69 785.47 8400 60.0 28.0 12.0 139 1000 0 0 1876.82 1921.44 983.03 5000 100.0 0.0 0.0 140 1000 700 300 2101.74 1923.11 872.24 9800 50.0 35.0 15.0 141 750 350 0 2596 1936.58 638.58 7200 68.2 31.8 0.0

Fit

Resp_(—)11=b0+b1*NF₃, sccm+b2*NF₃, sccm*NF₃, sccm+b3*C₃F₈, sccm*C₃F₈, sccm+b4*O₂, sccm*C₃F₈, sccm+b5*NF₃, sccm*CO₂, sccm

Summary |R| 0.874 R² 0.765 R² adjusted 0.658 Standard Error 306.26 # Points 17 PRESS 2709605.98 R² for Prediction 0.382 Durbin-Watson d 2.063 First Order Autocorrelation −0.225 Collinearity 0.003 Coefficient of Variation 15.923 Precision Index 23.627

The data for Formulation 2; Formulation 1; Pure NF₃ Comparison with low flow NF₃, are all shown in FIG. 19.

1. Formulation 2→

-   -   a. Primary etchant—COF₂     -   b. In-situ generation     -   c. Higher COF₂ generation due to more available F₂/molecule in         C₃F₈     -   d. Highest etch rate     -   e. Higher CF₄→inadequate CO₂ concentration     -   f. CF₄ formed from C₃F₈ breakdown in plasma

2. Formulation 1→

-   -   a. Primary etchant—COF₂     -   b. Lower etch rate     -   c. Lower COF₂ generation     -   d. Residual CO₂ (excess)     -   e. CF₄ formed from CO₂ and NF₃ breakdown in plasma

3. Pure NF₃→

-   -   a. Primary etchant—F₂     -   b. Lowest etch rate     -   c. No COF₂ or CF₄

Formulation 2; Formulation 1; Pure NF₃ Comparison with high flow NF₃ see FIG. 20

1. Formulation 2→

-   -   a. Primary etchant—COF₂     -   b. In-situ generation     -   c. Higher COF₂ generation due to more available F₂/molecule in         C₃F₈     -   d. Highest etch rate     -   e. Higher CF₄→inadequate CO₂ concentration     -   f. CF₄ formed from C₃F₈ breakdown in plasma

2, Formulation 1→

-   -   a. Primary etchant—COF₂     -   b. Lower etch rate     -   c. Lower COF₂ generation     -   d. Residual CO₂ (excess)     -   e. CF₄ formed from CO₂ and NF₃ breakdown in plasma

3. Pure NF₃→

-   -   a. Primary etchant—F₂     -   b. Lowest etch rate     -   c. No COF₂ or CF₄

Effect of CO₂ See FIGS. 21A-21C

1. NF₃+C₃F only→(see FIGS. 21A and 21B)

-   -   a. Primary etchant—F₂, C_(x)F_(y)*     -   b. Low etch rate     -   c. F₂ from NF₃ breakdown consumed by C_(x)F_(y) breakdown to         form CF₄ leading to low cleaning rates

2. NF₃+C₃F₈+CO₂→(see FIG. 21C)

-   -   a. Primary etchant—COF₂     -   b. In-situ generation

Effect of NF₃ Flow

1. For same available CO₂ and C₃F₈:

-   -   a. Lower NF₃ flow allows for marginally higher COF₂ generation     -   b. Higher NF₃ flow has lower COF₂ generation     -   c. CF₄ generation is similar and negligible compared to COF₂         generation.

Effect of Residence Time: High Residence Time—Experimental Run 2 See FIGS. 22A and 22B

1. Maximum etch rate of ˜2900 nm/min

-   -   a. 940 sccm NF₃     -   b. 700 sccm CO₂     -   c. 60 sccm C₃F₈

Effect of Residence Time: Lower Residence Time—Experimental Run 3 See FIGS. 23A and 23B

-   -   d. Maximum etch rate of ˜2400 nm/min in     -   e. Reduction of ˜20% compared to Higher residence times     -   f. Lower residence time=lower COF₂ generation

As used herein “substrate” may be a support substrate with or without layers formed thereon. The support substrate may be an insulator or a semiconductor of a variety of doping concentrations and profiles and may, for example, be a semiconductor substrate of the type used in the manufacture of integrated circuits. The term “precursor” is used to refer to any process gas which takes part in a reaction to either remove material from or deposit material onto a surface. A gas (or precursor) may be a combination of two or more gases (or precursors) and may include substances which are normally liquid or solid but temporarily carried along with other “matrix gases” or, synonymously, “carrier gases”. Matrix gases or carrier gases may be an “inert gas” which refers to any gas which does not form chemical bonds when etching or being incorporated into a film. Exemplary inert gases include noble gases but may include other gases so long as no chemical bonds are formed when (typically) trace amounts are trapped in a film.

Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the disclosed embodiments. Additionally, a number of well-known processes and elements have not been described in order to avoid unnecessarily obscuring the present invention. Accordingly, the above description should not be taken as limiting the scope of the invention.

Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a process” includes a plurality of such processes and reference to “the dielectric material” includes reference to one or more dielectric materials and equivalents thereof known to those skilled in the art, and so forth.

Also, the words “comprise,” “comprising,” “include,” “including,” and “includes” when used in this specification and in the following claims are intended to specify the presence of stated features, integers, components, or steps, but they do not preclude the presence or addition of one or more other features, integers, components, steps, acts, or groups. 

1. A method for generating carbonyl fluoride (COF₂) or its variants in-situ, comprising: exposing nitrogen trifluoride (NF₃), an oxygen source comprising a formula (CO_(x)) where x is 1 or 2, and a saturated, unsaturated or partially unsaturated perfluorocarbon compound comprising a formula (C_(y)F_(z)) to an energy source; dissociating the NF₃, CO_(x) and C_(y)F_(z) compounds thereby resulting in the fluorine/fluorine radicals and CO radicals; and forming COF₂ in-situ by recombination of the fluorine/fluorine radicals and CO radicals.
 2. The method of claim 1, wherein said energy source is from a plasma.
 3. The method of claim 1, wherein said energy source is electromagnetic radiation.
 4. The method of claim 1, wherein x=1 and said oxygen source is carbon monoxide (CO).
 5. The method of claim 1, wherein x=2 and said oxygen source is carbon dioxide (CO₂).
 6. The method of claim 1, wherein said saturated, unsaturated or partially unsaturated perfluorocarbon compound are selected from the group comprising C₃F₈, C₄F₈, C₂F₆, and C₄F₁₀.
 7. The method of claim 2, wherein nitrogen trifluoride (NF₃) is initially exposed to the energy source thereby igniting and sustaining an NF₃ plasma followed by the stepwise addition of an oxide of carbon (CO_(x)) and a perfluorocarbon compound (C_(y)F_(z)) or combinations thereof.
 8. The method of claim 2, wherein the method further comprises exposing argon (Ar) to said energy source thereby igniting a plasma in argon (Ar) and then adding nitrogen trifluoride (NF₃) to said argon thereby replacing the argon (Ar) to create an nitrogen trifluoride (NF₃) plasma followed by stepwise addition of an oxide of carbon (CO_(x)) and a perfluorocarbon compound (C_(y)F_(z)) mixtures to the nitrogen trifluoride (NF₃) plasma or combinations thereof.
 9. The method of claim 2, wherein the method further comprises exposing argon (Ar) to said energy source thereby igniting a plasma in argon (Ar) and then sustaining said plasma by stepwise addition of nitrogen trifluoride (NF₃), an oxide of carbon (CO_(x)) and a perfluorocarbon compound (C_(y)F_(z)) to the existing argon (Ar) plasma.
 10. The method of claim 2, wherein the method further comprises: introducing said oxide of carbon (CO_(x)) to argon prior to exposing argon (Ar) to said energy source; igniting a plasma in argon (Ar) having said oxide of carbon (CO_(x)) followed by the stepwise addition of nitrogen trifluoride (NF₃) and a perfluorocarbon compound (C_(y)F_(z)); stopping the flow of argon upon stabilization of said plasma.
 11. A method of cleaning a material with COF₂ produced in-situ, the method comprising: igniting and sustaining a nitrogen trifluoride (NF₃) plasma; introducing an oxide of carbon (CO_(x)) and a perfluorocarbon compound (C_(y)F_(z)) or combinations thereof in a stepwise fashion; forming COF₂ through the dissociation of the NF₃, CO_(x) and C_(y)F_(z) compounds and the in-situ recombination of said dissociated products; and reacting said COF₂ formed in-situ with a material existing in the proximity of COF₂ generation to produce volatile reaction products.
 12. The method of claim 11, wherein said material is selected from the group consisting of deposition of thin films of silicon, silicon oxides, silicon dioxides, silicon nitrides, poly-silicons, silicides, silicon carbo-nitride, silicon oxy-nitrides, and doped silicon glasses, TEOS, BPSG, doped oxides, metal nitrides, metal oxides, metals, metal compounds, semiconductor substrates, PV substrates, LED/OLED, MOCVD substrates, III-V materials.
 13. The method of claim 11, wherein the method further comprises optimizing reaction rate with said material by varying the residence times, pressures and flow conductances of the interaction environment or combinations thereof.
 14. The method of claim 11, wherein forming COF₂ results in the cleaning of a substrate in the proximity of said COF₂ wherein contaminants are removed from the substrate.
 15. A method for generating carbonyl fluoride (COF₂) or its variants in-situ, comprising: exposing NF₃, CO₂, and a saturated, unsaturated or partially unsaturated perfluorocarbon (PFC) compound to an energy source in a stepwise fashion; dissociating the NF₃, CO₂ and PFC compounds thereby resulting in the fluorine/fluorine radicals and CO radicals; and forming COF₂ in-situ by recombination of the fluorine/fluorine radicals and CO radicals.
 16. The method of claim 15, wherein NF₃ is initially exposed to the energy source thereby igniting and sustaining an NF₃ plasma followed by the stepwise addition of CO₂ and PFC.
 17. The method of claim 15, wherein the NF₃ may be excited in a plasma 2 inside a chamber or in a remote plasma region upstream from said chamber.
 18. The method of claim 15, further comprises introducing NF₃, CO₂, and a saturated, unsaturated or partially unsaturated perfluorocarbon (PFC) compound to a chamber after, or contemporaneously with activation by an energy source, wherein the by-products are removed from the chamber.
 19. The method of claim 15, wherein said energy source is from plasma
 20. The method of claim 15, wherein said energy source is electromagnetic radiation.
 21. The method of claim 16, wherein the method further comprises exposing argon (Ar) to said energy source thereby igniting a plasma in argon (Ar) and then adding a mixture of argon/nitrogen trifluoride (NF₃) to said argon thereby replacing the argon (Ar) to create an argon/nitrogen trifluoride (NF₃) plasma followed by stepwise replacement of an oxide of carbon (CO_(x)) to the nitrogen trifluoride (NF₃) plasma or combinations thereof.
 22. The method of claim 16, wherein the method further comprises exposing argon (Ar) to said energy source thereby igniting a plasma in argon (Ar) and then adding a mixture of argon/nitrogen trifluoride (NF₃) to said argon thereby replacing the argon (Ar) to create an argon/nitrogen trifluoride (NF₃) plasma followed by stepwise replacement of an oxide of carbon (CO_(x)) and a perfluorocarbon compound (C_(y)F_(z)) mixtures to the nitrogen trifluoride (NF₃) plasma or combinations thereof. 